Unbridged monocyclopentadienyl metal complex catalyst and a process for polyolefin production

ABSTRACT

There is provided a catalyst containing a transition metal precursor having the formula (C5R15)MX3, an alcohol, a substituted bulky phenol, an aluminoxane, and optionally a support or spray drying material. There is also provided a polymerization process employing the catalyst composition, a polymer produced using the catalyst, and a cable produced therefrom.

This is a divisional of application Ser. No. 08/987,753 filed Dec. 9,1997, now U.S. Pat. No. 5,962,362.

FIELD OF THE INVENTION

The invention relates to a catalyst composition for olefinpolymerization and a process for polymerizing polyolefins, especiallycopolymers of ethylene-alpha olefins, ethylene-alpha olefin-dienes, andpolypropylene using a metallocene catalyst. More particularly, theinvention concerns the polymerization of polyolefins having less than50% crystallinity using a metallocene catalyst containing a transitionmetal and an aluminoxane.

BACKGROUND OF THE INVENTION

There has been a growing interest in the use of metallocenes forpolyolefin production. Many metallocenes for polyolefin production aredifficult and time-consuming to prepare, require large amounts ofalumoxane, and exhibit poor reactivity toward higher olefins, especiallyfor making ethylene-alpha olefin copolymers and ethylene-alphaolefin-diene terpolymers. Moreover, the ethylene-alpha olefin copolymersand ethylene-alpha olefin-diene terpolymers prepared using thesemetallocenes often have undesirably low molecular weights (i.e., Mw lessthat 50,000).

The so-called “constrained geometry” catalysts such as those disclosedin EP 0 420 436 and EP 0 416 815 can provide a high comonomer responseand a high molecular weight copolymer, but are difficult to prepare andpurify, and, therefore, are expensive. Another drawback of the bridgedamido-cyclopentadienyl titanium catalyst system is that in order to forman active oxide-supported catalyst, it is necessary to use fairly highlevels of alumoxane (see, e.g., WO96/16092) or to employ mixtures ofaluminum alkyl and an activator based on derivatives oftris(pentafluorophenyl)borane (see, e.g., WO95/07942), itself anexpensive reagent, thus raising the cost of running the catalyst. In theconstrained geometry catalyst art, such as the angle formed by thecyclopentadienyl centroid, transition metal, and amide nitrogen iscritical to catalyst performance. Indeed, comparison of the publishedresult using a bridged amido-cyclopentadienyl titanium systems withsimilar unbridged systems has generally shown the unbridged analogs tobe relatively inactive. One such system, described in U.S. Pat. No.5,625,016 shows very low activity, while having some of the desirablecopolymerization behavior.

In contrast to the constrained geometry catalysts, the catalyst of theinvention is unconstrained or unbridged and relatively easily andinexpensively prepared using commercially available starting materials.Further, the level of aluminoxane utilized can be lowered. That is, inthe present invention, the precursor can be dried onto a support or witha spray drying material with Al:Ti ratios below 100:1 to form highlyactive catalysts with similar polymerization behavior to theirunsupported analogs of the invention and polymerization behavior similarto constrained catalysts.

In Idemitsu Kosan JPO 8/231622, it is reported that the active catalystmay be formed starting from (C₅Me₅)Ti(OMe)₃ and that the polymer formedhas a relatively wide or broad compositional distribution. The presentinvention does not utilize this precursor.

Typically, polyolefins such as EPRs and EPDMs are produced commerciallyusing vanadium catalysts. In contrast to polyolefins produced usingvanadium catalysts, those produced by the catalysts of the presentinvention have high molecular weight and narrower compositiondistribution (i.e., lower crystallinity at an equivalent alpha olefincontent.

There is an on-going need to provide a catalyst employing a metallocenewhich is easy to prepare, does not require large amounts of aluminoxaneand which readily copolymerizes to produce ethylene-alpha olefincopolymers, ethylene-alpha olefin-diene terpolymers, and polypropylene,as well as producing polyethylene.

SUMMARY OF THE INVENTION

Accordingly, the present invention provides a catalyst comprising:

(A) a transition metal compound having the formula: (C₅R¹ ₅)MX₃, whereineach R¹ substituent is independently selected from the group consistingof hydrogen, a C₁-C₈ alkyl, an aryl, and a heteroatom-substituted arylor alkyl, with the proviso that no more than three R¹ substituents arehydrogen; and wherein two or more R¹ substituents may be linked togetherforming a ring; M is a transition metal of Group IVB of the PeriodicTable of the Elements; and X is a halide atom (F, Br, Cl, or I);

(B) a compound having the formula: R²OH, wherein R² is a C₁-C₈ alkyl;

(C) a bulky phenol compound having the formula: (C₆R³ ₅)OH, wherein eachR³ group is independently selected from the group consisting ofhydrogen, halide, a C₁-C₈ alkyl, an aryl, a heteroatom substituted alkylor aryl, wherein two or more R³ groups may be linked together forming aring, and in which at least one R³ is represented by a C₃-C₁₂ linear orbranched alkyl located at either or both the 2 and 6 position (i.e., theortho positions relative to the OH group being in position 1) of thebulky phenol compound; and

(D) an aluminoxane.

There is also provided a polymerization process employing the catalystcomposition and a polymer produced using the catalyst. A cablecomposition is also provided.

DETAILED DESCRIPTION OF THE INVENTION

Catalyst

The catalyst contains a transition metal precursor (Component A), analcohol (Component B), a substituted bulky phenol (Component C), analuminoxane (Component D). The catalyst of the invention can beunsupported (that is, in liquid form), supported, spray dried, or usedas a prepolymer. Support and/or spray drying material is described asoptional Component E.

Component A is a transition metal compound having the formula: (C₅R¹₅)MX₃, wherein each R¹ substituent is independently selected from thegroup consisting of hydrogen, a C₁-C₈ alkyl, an aryl, and aheteroatom-substituted aryl or alkyl, with the proviso that no more thanthree R¹ substituents are hydrogen; and wherein two or more R¹substituents may be linked together forming a ring; M is a transitionmetal of Group IVB of the Periodic Table of the Elements; and X is ahalide atom (F, Br, Cl, or I). Transition metals can include, forexample, titanium, zirconium, and hafnium. Preferably, the transitionmetal, M, is titanium. Illustrative titanium compounds can include:pentamethylcyclopentadienyltitanium trichloride;pentamethylcyclopentadienyltitanium tribromide;pentamethylcyclopentadienyltitanium triiodide;1,3-bis(trimethylsilyl)cyclopentadienyl-titanium trichloride;tetramethylcyclopentadienyltitanium trichloride; fluorenyltitaniumtrichloride; 4,5,6,7-tetrahydroindenyltitanium trichloride;1,2,3,4,5,6,7,8-octahydro-fluorenyltitanium trichloride;1,2,3,4-tetrahydrofluorenyl-titanium trichloride;1,2,3-trimethylcyclopentadienyltitanium trichloride;1,2,4-trimethylcyclopentadienyltitanium trichloride;1-n-butyl-3-methyl-cyclopentadienyltitanium trichloride;methylindenyltitanium trichloride; 2-methylindenyltitanium trichloride;and 4,5,6,7-tetrahydro-2-methylindenyltitanium trichloride. Illustrativezirconium and hafnium compounds useful in the catalyst precursor of theinvention by replacing titanium in the above-enumerated compounds withzirconium and hafnium. In the precursor, a heteroatom is an atom otherthan carbon (e.g, oxygen, nitrogen, sulfur and so forth) in the ring ofthe heterocyclic moiety.

Component B is an alcohol having the formula: R²OH, wherein R² is aC₁-C₈ alkyl. Illustrative R²OH compounds in which R² is alkyl caninclude, for example, methanol, ethanol, propanol, butanol (including n-and t-butanol), pentanol, hexanol, heptanol, octanol. Preferably, R² isa methyl group.

Component C is a bulky phenol compound having the formula: (C₆R³ ₅)OH,wherein each R³ group is independently selected from the groupconsisting of hydrogen, halide, a C₁-C₈ alkyl, an aryl, a heteroatomsubstituted alkyl or aryl, wherein two or more R³ groups may be linkedtogether forming a ring, and in which at least one R³ is represented bya C₃-C₁₂ linear or branched alkyl located at either or both the 2 and 6position (i.e., the ortho positions relative to the OH group being inposition 1) of the bulky phenol compound;. In the formula, preferablynone of the R³ groups is a methoxy group. Preferably, suitable R³ groupscan include, for example, t-butyl, isopropyl, n-hexyl and mixturesthereof.

Component D is a cocatalyst capable of activating the catalyst precursoris employed as Component D. Preferably, the activating cocatalyst is alinear or cyclic oligomeric poly(hydrocarbylaluminum oxide) whichcontain repeating units of the general formula —(Al(R*)O)—, where R* ishydrogen, an alkyl radical containing from 1 to about 12 carbon atoms,or an aryl radical such as a substituted or unsubstituted phenyl ornaphthyl group. More preferably, the activating cocatalyst is analuminoxane such as methylaluminoxane (MAO) or modifiedmethylaluminoxane (MMAO).

Aluminoxanes are well known in the art and comprise oligomeric linearalkyl aluminoxanes represented by the formula:

and oligomeric cyclic alkyl aluminoxanes of the formula:

wherein s is 1-40, preferably 10—20; p is 3-40, preferably 3-20; andR*** is an alkyl group containing 1 to 12 carbon atoms, preferablymethyl.

Aluminoxanes may be prepared in a variety of ways. Generally, a mixtureof linear and cyclic aluminoxanes is obtained in the preparation ofaluminoxanes from, for example, trimethylaluminum and water. Forexample, an aluminum alkyl may be treated with water in the form of amoist solvent. Alternatively, an aluminum alkyl, such astrimethylaluminum, may be contacted with a hydrated salt, such ashydrated ferrous sulfate. The latter method comprises treating a dilutesolution of trimethylaluminum in, for example, toluene with a suspensionof ferrous sulfate heptahydrate. It is also possible to formmethylaluminoxanes by the reaction of a tetraalkyldialuminoxanecontaining C₂ or higher alkyl groups with an amount of trimethylaluminumthat is less than a stoichiometric excess. The synthesis ofmethylaluminoxanes may also be achieved by the reaction of a trialkylaluminum compound or a tetraalkyldialuminoxane containing C₂ or higheralkyl groups with water to form a polyalkyl aluminoxane, which is thenreacted with trimethylaluminum. Further, modified methylaluminoxanes,which contain both methyl groups and higher alkyl groups, i.e., isobutylgroups, may be synthesized by the reaction of a polyalkyl aluminoxanecontaining C₂ or higher alkyl groups with trimethylaluminum and thenwith water as disclosed in, for example, U.S. Pat. No. 5,041,584.

The mole ratio of aluminum atoms contained in thepoly(hydrocarbylaluminum oxide) to total metal atoms contained in thecatalyst precursor is generally in the range of from about 2:1 to about100,000:1, preferably in the range of from about 10:1 to about 10,000:1,and most preferably in the range of from about 50:1 to about 2,000:1.

Preferably, Component D is an alumoxane of the formula (AlR⁵O )m(AlR⁶O)nin which R⁵ is a methyl group, R⁶ ⁵is a C₁-C₈ alkyl, m ranges from 3 to50; and n ranges from 1 to 20. Most preferably, R⁶ is a methyl group.

Component E

Optionally, one or more of the above-described catalyst components maybe impregnated in or deposited on a support, or alternatively spraydried with a support material. These support or spray drying materialsare typically solid materials which are inert with respect to the othercatalyst components and/or reactants employed in the polymerizationprocess. Suitable support or spray drying materials can include silica,carbon black, polyethylene, polycarbonate, porous crosslinkedpolystyrene, porous crosslinked polypropylene, alumina, thoria, titania,zirconia, magnesium halide (e.g., magnesium dichloride), and mixturesthereof. Preferred among these support materials are silica, alumina,carbon black, and mixtures thereof. These are composed of porousparticulate supports that usually have been calcined at a temperaturesufficient to remove substantially all physically bound water.

The molar ratio of Component B to Component A ranges from about 2:1 to200:1; preferably about 2:1 to 50:1; and, most preferably, is about 2:1to 20:1. The molar ratio of Component C to Component A ranges from about5:1 to 1000:1; preferably about 10:1 to 300:1; and, most preferably isabout 30:1 to 200:1. The molar ratio of Component D to Component Aranges from about 10:1 to 10,000:1, preferably about 30:1 to 2,000:1,and most preferably, is about 50:1 to 1000:1, with the provisos that (1)the ratio of Component B to Component D does not exceed 0.7:1, and ispreferably between 0.001:1 to 0.050:1; and (2) the ratio of Component Cto Component D does not exceed 1:1, and is preferably below 0.7:1. WhenComponent E is employed as a support or spray drying material, it isemployed in an amount ranging from about 7 to 200 g/mmol, preferably 12to 100 g/mmol, and most preferably 20 to 70 g/mmol (grams of Component Eper millimole Component A).

Process for Making the Catalyst

The individual catalyst components (Components A, B, C, D and optionallyE) can be combined in any order prior to polymerization. Alternatively,the individual catalyst components can be fed to the polymerizationreactor such that the catalyst is formed in-situ.

Preferably, the active catalyst is prepared as follows. In Step 1,Components A and B are mixed in an inert hydrocarbon solvent suitablefor dissolving Components A through D under an inert atmosphere (e.g.,nitrogen) for at least 15 minutes or longer (e.g., up to 3 days). Thecomponents are combined such that Component A is mixed with at leastthree molar equivalents of Component B. Typical inert solvents caninclude, for example, toluene, xylene, chlorobenzene, etc. Preferredamong these solvents is toluene.

In Step 2, Component C is mixed with Component D in one of theabove-described inert hydrocarbon solvents, preferably the same solventemployed in Step 1, under an inert atomosphere (e.g., nitrogen and/orargon) for at least 15 minutes or longer (e.g., for up to 3 days). Theratio of aluminum (in the aluminoxane, Component D) to phenol of thebulky phenol compound (Component C) ranges from 1.4:1 to 1000:1;preferably 3:1 to 100:1; most preferably 3:1 to 10:1.

Optionally, the support or spray drying material (Component E) can beadded to any of the above-described solutions, mixtures, and/orslurries. When Component E is employed the mixing should take place forabout 30 minutes or more and the ratio of aluminum to support materialis in the range of about 0.5 to 10 mmol./g., preferably, 2 to 5 mmol./g.

In Step 3, the mixture of Components A and B is combined with themixture of Components C and D (and optional E) in such proportion thatthe molar ratio of aluminum to transition metal is about 5 to 5000,preferably 30 to 1000, and the molar ratio of Component B to aluminum isless than 0.5. The mixture is stirred for at least about 5 minutes. Themixture can be used as a liquid for direct injection into thepolymerization reactor, or, if Component E is present, may be dried invacuo to a free-flowing powder or spray-dried in an inert atmosphere. IfComponent E is not present, the catalyst is then fed to the reactor inliquid form. If Component E is present and the catalyst is in solidform, it may be introduced into the reactor by a variety of methodsknown to those skilled in the art such as by inert gas conveyance or byinjection of a mineral oil slurry of the catalyst.

Polymerization Process and Conditions

The above-described catalyst composition can be used for thepolymerization of monomers (e.g., olefins, diolefins, and/or vinylaromatic compounds) in a suspension, solution, slurry, or gas phaseprocess using known equipment and reaction conditions, and it is notlimited to any specific type of reaction. However, the preferredpolymerization process is a gas phase process employing a fluidized bed.Gas phase processes employable in the present invention can includeso-called “conventional” gas phase processes, “condensed-mode,” and,most recent, “liquid-mode” processes.

In many processes, it is desirable to include a scavenger in the reactorto remove adventitious poisons such as water or oxygen before they canlower catalyst activity. In such cases, it is recommended thattrialkylaluminum species not be used, but rather that methylalumoxane beemployed for such purposes.

Conventional fluidized processes are disclosed, for example, in U.S.Pat. Nos. 3,922,322; 4,035,560; 4,994,534, and 5,317,036.

Condensed mode polymerizations, including induced condensed mode, aretaught, for example, in U.S. Pat. Nos. 4,543,399; 4,588,790; 4,994,534;5,317,036; 5,352,749; and 5,462,999. For polymerizations producing alphaolefin homopolymers and copolymers condensing mode operation ispreferred.

Liquid mode or liquid monomer polymerization mode is described in U.S.Pat. No. 4,453,471; U.S. Ser. No. 510,375; and WO 96/04322(PCT/US95/09826) and WO 96/04323 (PCT/US95/09827). For polymerizationssuch as ethylene-propylene copolymer (e.g., EPMs),ethylene-propylene-diene terpolymer (e.g., EPDMs), and diolefin (e.g.,butadiene) polymerizations, it is preferable to use liquid mode and toemploy an inert particulate material, a so-called fluidization aid.Inert particulate materials are described, for example, in U.S. Pat. No.4,994,534 and include carbon black, silica, clay, talc, and mixturesthereof. Of these, carbon black, silica, and mixtures of them arepreferred. When employed as fluidization aids, these inert particulatematerials are used in amounts ranging from about 0.3 to about 80% byweight, preferably about 5 to 50% based on the weight of the polymerproduced. The use of inert particulate materials as fluidization aids inpolymer polymerization produces a polymer having a core-shellconfiguration such as that disclosed in U.S. Pat. No. 5,304,588. Thecatalyst of the invention in combination with one or more of thesefluidization aids produces a resin particle comprising an outer shellhaving a mixture of a polymer and an inert particulate material, whereinthe inert particulate material is present in the outer shell in anamount higher than 75% by weight based on the weight of the outer shell;and an inner core having a mixture of inert particulate material andpolymer, wherein the polymer is present in the inner core in an amounthigher than 90% by weight based on the weight of the inner core. In thecase of sticky polymers, these resin particles are produced by afluidized bed polymerization process at or above the softening point ofthe sticky polymer.

The polymerizations can be carried out in a single reactor or multiplereactors, typically two or more in series, can also be employed. Theessential parts of the reactor are the vessel, the bed, the gasdistribution plate, inlet and outlet piping, at least one compressor, atleast one cycle gas cooler, and a product discharge system. In thevessel, above the bed, there is a velocity reduction zone, and in thebed a reaction zone.

Generally, all of the above modes of polymerizing are carried out in agas phase fluidized bed containing a “seed bed” of polymer which is thesame or different from the polymer being produced. Preferably, the bedis made up of the same granular resin that is to be produced in thereactor.

The bed is fluidized using a fluidizing gas comprising the monomer ormonomers being polymerized, initial feed, make-up feed, cycle (recycle)gas, inert carrier gas (e.g., nitrogen, argon, or inert hydrocarbon suchas ethane, propane, isopentane) and, if desired, modifiers (e.g.,hydrogen). Thus, during the course of a polymerization, the bedcomprises formed polymer particles, growing polymer particles, catalystparticles, and optional flow aids (fluidization aids) fluidized bypolymerizing and modifying gaseous components introduced at a flow rateor velocity sufficient to cause the particles to separate and act as afluid.

In general, the polymerization conditions in the gas phase reactor aresuch that the temperature can range from sub-atomospheric tosuper-atmospheric, but is typically from about 0 to 120° C., preferablyabout 40 to 100° C., and most preferably about 40 to 80° C. Partialpressure will vary depending upon the particular monomer or monomersemployed and the temperature of the polymerization, and it can rangefrom about 1 to 300 psi (6.89 to 2,0067 kiloPascals), preferably 1 to100 psi (6.89 to 689 kiloPascals). Condensation temperatures of themonomers such as butadiene, isoprene, styrene are well known. Ingeneral, it is preferred to operate at a partial pressure slightly aboveto slightly below (that is, for example, +10° C. for low boilingmonomers) the dew point of the monomer.

Polymers Produced

Olefin polymers that may be produced according to the invention include,but are not limited to, ethylene homopolymers, homopolymers of linear orbranched higher alpha-olefins containing 3 to about 20 carbon atoms, andinterpolymers of ethylene and such higher alpha-olefins, with densitiesranging from about 0.84 to about 0.96. Homopolymers and copolymers ofpropylene can also be produced by the inventive catalyst and process.Suitable higher alpha-olefins include, for example, propylene, 1-butene,1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and3,5,5-trimethyl-1-hexene. Preferably, the olefin polymers according tothe invention can also be based on or contain conjugated ornon-conjugated dienes, such as linear, branched, or cyclic hydrocarbondienes having from about 4 to about 20, preferably 4 to 12, carbonatoms. Preferred dienes include 1,4-pentadiene, 1,5-hexadiene,5-vinyl-2-norbornene, 1,7-octadiene, 7-methyl-1,6-octadiene, vinylcyclohexene, dicyclopentadiene, butadiene, isobutylene, isoprene,ethylidene norbornene and the like. Aromatic compounds having vinylunsaturation such as styrene and substituted styrenes, and polar vinylmonomers such as acrylonitrile, maleic acid esters, vinyl acetate,acrylate esters, methacrylate esters, vinyl trialkyl silanes and thelike may be polymerized according to the invention as well. Specificolefin polymers that may be made according to the invention include, forexample, polyethylene, polypropylene, ethylene/propylene rubbers(EPR's), ethylene/pro-pylene/diene terpolymers (EPDM's), polybutadiene,polyisoprene, and the like.

The present invention provides a cost-effective catalyst and method formaking compositionally homogeneous, high-molecular weight ethylene-alphaolefin copolymers with very high levels of alpha olefin. One advantageis that the catalyst has a very high comonomer response, so the ratio ofalpha olefin to ethylene present in the reaction medium can be very low,which increases the partial pressure of ethylene possible in thereactor. This improves catalyst activity. It also lessens the level ofresidual comonomer which must be purged or otherwise recovered from thepolymer after it exits the reactor. The catalyst is also suitable forincorporation of non-conjugated dienes to form completely amorphousrubbery or elastomeric compositions. The catalyst's very high comonomerresponse also makes it a good candidate for the incorporation oflong-chain branching into the polymer architecture through the insertionof vinyl-ended polymer chains formed via β-hydride elimination. Theethylene copolymers produced by the present invention havepolydespersity values (PDI) ranging from 2 to 4.6, preferably 2.6 to4.2.

Polymers produced using the catalyst and/or process of the inventionhave utility in wire and cable applications, as well as in otherarticles such as molded and extruded articles such as hose, belting,roofing materials, tire components (tread, sidewall inner-liner,carcass, belt). Polyolefins produced using the catalyst and/or processof the invention can be cross-linked, vulcanized or cured usingtechniques known to those skilled in the art.

In particular, there is provided by the invention a cable comprising oneor more electrical conductors, each, or a core of electrical conductors,surrounded by an insulating composition comprising a polymer produced ina gas phase polymerization process using the catalyst of the invention.Preferably, the polymer is polyethylene; a copolymer of ethylene, one ormore alpha-olfins having 3 to 12 carbon atoms, and, optionally, adiene(s).

Conventional additives, which can be introduced into the cable and/orpolymer formulation, are exemplified by antioxidants, coupling agents,ultraviolet absorbers or stabilizers, antistatic agents, pigments, dyes,nucleating agents, reinforcing fillers or polymer additives, slipagents, plasticizers, processing aids, lubricants, viscosity controlagents, tackifiers, anti-blocking agents, surfactants, extenders oils,metal deactivators, voltage stabilizers, flame retardant fillers andadditives, crosslinking agents, boosters, and catalysts, and smokesuppressants. Fillers and additives can be added in amounts ranging fromless than about 0.1 to more than about 200 parts by weight for each 100parts by weight of the base resin, for example, polyethylene.

Examples of antioxidants are: hindered phenols such astetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane,bis[(beta-(3,5di-tert-butyl-4-hydroxybenzyl)-methylcarboxyethyl)]sulphide,4,4′-thiobis(2-methyl-6-tert-butylphenol), 4,4′-thiobis(2-tert-butyl-5-methylphenol),2,2′-thiobis(4-methyl-6-tert-butylphenol), and thiodiethylene bis(3,5ditert-butyl-4-hydroxy)hydrocinnamate; phosphites and phosphonites suchas tris(2,4-di-tert-butylphenyl) phosphite anddi-tert-butylphenyl-phosphonite; thio compounds such asdilaurylthiodipropionate, dimyristylthiodipropionate, anddistearylthiodipropionate; various siloxanes; and various amines such aspolymerized 2,2,4-trimethyl-1,2-dihyroquinoline. Antioxidants can beused in amounts of about 0.1 to about 5 parts by weight per 100 parts byweight of polyethylene.

The resin can be crosslinked by adding a crosslinking agent to thecomposition or by making the resin hydrolyzable, which is accomplishedby adding hydrolyzable groups such as —Si(OR)₃ wherein R is ahydrocarbyl radical to the resin structure through copolymerization orgrafting.

Suitable crosslinking agents are organic peroxides such as dicumylperoxide; 2,5-dimethyl-2,5-di(t-butylperoxy) hexane; t-butyl cumylperoxide; and 2,5-dimethyl-2,5-di(t-butylperoxy)hexane-3. Dicumylperoxide is preferred.

Hydrolyzable groups can be added, for example, by copolymerizingethylene with an ethylenically unsaturated compound having one or more—Si(OR)₃ groups such as vinyltrimethoxy- silane, vinyltriethoxysilane,and gamma-methacryloxypropyltrimethoxysilane or grafting these silanecompounds to the resin in the presence of the aforementioned organicperoxides. The hydrolyzable resins are then crosslinked by moisture inthe presence of a silanol condensation catalyst such as dibutyltindilaurate, dioctyltin maleate, dibutyltin diacetate, stannous acetate,lead naphthenate, and zinc caprylate. Dibutyltin dilaurate is preferred.

Examples of hydrolyzable copolymers and hydrolyzable grafted copolymersare ethylene/vinyltrimethoxy silane copolymer,ethylene/gamma-methacryloxypropyltrimethoxy silane copolymer,vinyltrimethoxy silane grafted ethylene/ethyl acrylate copolymer,vinyltrimethoxy silane grafted linear low density ethylene/1-butenecopolymer, and vinyltrimethoxy silane grafted low density polyethylene.

The cable and/or polymer formulation can contain a polyethylene glycol(PEG) as taught in EP 0 735 545.

The cable of the invention can be prepared in various types ofextruders, e.g., single or twin screw types. Compounding can be effectedin the extruder or prior to extrusion in a conventional mixer such asBrabender™ mixer or Banbury™ mixer. A description of a conventionalextruder can be found in U.S. Pat. No. 4,857,600. A typical extruder hasa hopper at its upstream end and a die at its downstream end. The hopperfeeds into a barrel, which contains a screw. At the downstream end,between the end of the screw and the die, is a screen pack and a breakerplate. The screw portion of the extruder is considered to be divided upinto three sections, the feed section, the compression section, and themetering section, and two zones, the back heat zone and the front heatzone, the sections and zones running from upstream to downstream. In thealternative, there can be multiple heating zones (more than two) alongthe axis running from upstream to downstream. If it has more than onebarrel, the barrels are connected in series. The length to diameterratio of each barrel is in the range of about 15:1 to about 30:1. Inwire coating, where the material is crosslinked after extrusion, the dieof the crosshead feeds directly into a heating zone, and this zone canbe maintained at a temperature in the range of about 130° C. to about260° C., and preferably in the range of about 170° C. to about 220° C.

All references cited herein are incorporated by reference.

Whereas the scope of the invention is set forth in the appended claims,the following specific examples illustrate certain aspects of thepresent invention. The examples are set forth for illustration only andare not to be construed as limitations on the invention, except as setforth in the claims. All parts and percentages are by weight unlessotherwise specified.

EXAMPLES GLOSSARY AND ABBREVIATIONS

BHA: 2,6-di-t-butyl-4-methoxyphenol

BHT: 2,6-di-t-butyl-4-methylphenol

C₃═:C₂═, fill: ratio of propylene to ethylene in the pressurizationstage of the polymerization

C₃═:C₂═, feed: ratio of propylene to ethylene in the period betweenpressurization and termination

DSC: differential scanning calorimetry

DTBP: 2,6-di-t-butylphenol

ENB: 5-ethylidene-2-norbornene

FI: flow index, ASTM standard I₂₁, in dg/min

ICP: inductively coupled plasma method for elemental analysis

Irganox Irganox 1076, a product of Ciba-Geigy

Kemamine Kemamine AS-990, a product of Witco Corp.

MAO: methylalumoxane (Ethyl/Albemarle, solution in toluene, 1.8 or 3.6moles Al/L)

PDI: polydispersity index, or M_(w)/M_(n)

PRT: peak recrystallization temperature, or the exothermic peak of thecooling trace in a DSC experiment, in degrees Celsius

SEC: size-exclusion chromatography method for molecular weightestimation

TBC: 2-t-butyl-4-methylphenol

TiBA triisobutylaluminum, 0.87 mol/L in hexanes

TTBP: 2,4,6-tri-t-butylphenol

Materials

Cyclopentadienyltitanium trichloride was obtained from Aldrich ChemicalCo. and was used without further purification.Pentamethylcyclopentadienyltitanium trichloride and indenyltitaniumtrichloride were obtained from Strem Chemicals Inc., and also usedwithout further purification. Methylalumoxane was purchased from theEthyl Corporation or the Albemarle Corporation and had a nominalconcentration of 1.8 mol(Al)/L.(1,3-bis(trimethylsilyl)cyclopentadienyl)titanium trichloride wasprepared according to a literature procedure [Jutzi, P.; Kuhn, M. J.Organomet. Chem., vol. 173 (1979), p. 221].

Procedure for Estimation of Propylene Content by Infrared Spectroscopy

Thin polymer samples for spectroscopy were prepared either by casting ahexane solution of the polymer onto a disk of potassium bromide and thenallowing the sample to dry or by placing a small amount of polymerbetween two sheets of poly(ethylene terephthalate) film and subjectingthe polymer to pressure and melting temperatures. A Nicolet® Model 510IR spectrometer was used to acquire the IR spectrum, with 32 scans foreach sample and background spectrum and 4 cm⁻¹ resolution. Peak heights,suitably corrected for baseline absorbance, were measured at thefollowing frequencies: 722, 1155, 1380, 1685, and 4250 cm-⁻¹. If theabsorbance at 1380 cm⁻¹ was less than 2.5, then the propylene contentwas calculated as follows:${{{wt}\quad \% \quad C_{\overset{=}{3}}} = {21.8 - \left( {{15.4 \cdot \ln}\quad \left( \frac{A_{722}}{A_{1380}} \right)} \right)}};$

Otherwise, the propylene content was estimated by the followingrelationship:${{wt}\quad \% \quad C_{\overset{=}{3}}} = {70.9 - {\left( {{18.7 \cdot \ln}\quad \left( \frac{A_{722}}{A_{1155}} \right)} \right).}}$

If ENB was present in the polymer, the weight fraction thereof wasestimated by the following:${{wt}\quad \% \quad {ENB}} = {0.04161 + {\left( \frac{13.336 \cdot A_{1685}}{A_{4250}} \right).}}$

Example 1

A small glass vial was charged with magnetic stirbar and a toluene (HPLCgrade, previously held over dried molecular sieves and sparged withnitrogen) solution of (C₅Me₅)TiCl₃ (0.0036 mmol/L) and methanol (0.014mmol/L). A solution of DTBP in toluene (0.104 mol/L) was prepared. A 120mL glass bottle equipped with stirbar was then charged with 50 mLhexanes (previously dried by 13× molecular sieves and sparged withnitrogen) under nitrogen, followed by 1 mmol of MAO as toluene solution,then DTBP solution, such that DTBP/MAO=0.1. After stirring forapproximately 5 min, 0.28 mL of the (C₅Me₅)TiCl₃/methanol solution(0.001 mmol Ti) was injected into the hexane solution. The mixture wastransferred by nitrogen overpressure into a 1.3 L stainless-steelreactor (Fluitrons®) which had been dried by flowing nitrogen through itwhile it was held at 100° C. for at least 1 hour (h.). The reactor had aremovable two-baffle insert and a variable speed propeller-shapedimpeller, which was run at 800 rpm. Following the introduction of thehexane solution of the catalyst mixture, an additional 600 mL hexaneswere transferred into the reactor. The reactor was sealed and heated to60° C., where it was held throughout the remainder of the run by acombination of cold water and steam flowed through the reactor jacket.When the reactor had reached approximately 40° C., the reactor wasvented of most of the nitrogen, resealed, and pressurized with 101 psig(0.70 MPa) of a mixture of propylene and ethylene, with the propyleneflow made to equal that of ethylene, both measured in L/min. When thereactor had reached within ca. 0.03 MPa of the final pressure, the ratioof propylene to ethylene flows was adjusted to 1:3. The polymerizationcontinued until 30 min after the introduction of monomer gases, at whichpoint the reactor was vented and the temperature rapidly cooled to roomtemperature. The polymer was recovered by transfer of the polymersolution to a large glass beaker, to which were added ca. 500 mL of a1:1 mixture by volume of methanol and 2-propanol. The recovered polymerweighed 11.6 g, for a catalyst activity of 23.2 kg(EPR)/(mmol(Ti).h).The polymer contained 43 weight % propylene by IR spectroscopy and hadFI=0.36. SEC found the Mw=420,100, with PDI=2.8. DSC on the polymerrevealed a crystallinity of 0.83% on first heat and a PRT of −21.3° C.

Examples 2-16

Polymerizations were conducted at 60° C. in 650 mL hexanes. Otherconditions and results are set forth in Table I.

Comparative Example C1-C4

Polymerizations were conducted at 60° C. in 650 mL hexanes. Otherconditions and results are combined in Table I.

Example 17

In a glovebox under nitrogen, a small glass vial was charged withmagnetic stirbar and 0.0145 g of (C₅Me₅)TiCl₃. The vial was sealed andbrought out of the glovebox, where 5 mL toluene (Aldrich anhydroustoluene, packaged under nitrogen) was added via syringe, to form a(C₅Me₅)TiCl₃/toluene solution with concentration of 0.01 mol/L. Inanother small glass vial sealed under nitrogen, 0.05 mL of methanol wasadded followed by 10 mL of same toluene to form a MeOH/Toluene solutionwith the concentration of 0.123 mol/L. In another small glass vialsealed under nitrogen, 2.06 g of 2,6-di-t-butylphenol (DTBP) was addedfollowed by 20 mL of toluene to form a DTBP solution with concentrationof 0.5 mol/L.

A small glass vial with stirbar was sealed under nitrogen. To this smallvial, 0.5 mL of (C₅Me₅)TiCl₃/toluene solution was charged with syringe(0.005 mmol Ti) followed by 0.16 mL of MeOH/toluene solution for a molarratio of methanol to titanium of 4. This solution mixture was stirred atroom temperature for 60 minutes.

A 100 mL glass bottle was charged with a stirbar and purged withnitrogen and then sealed with septum under nitrogen. To this bottle, 50mL hexane was added followed by 0.71 mL MAO solution (3.5 mol/L intoluene). 1.0 mL DTBP solution in toluene (0.5 mol/L) was also added tothis bottle followed by 2 mL of ENB. After this, 0.66 mL of(C₅Me₅)TiCl₃/MeOH mixture solution was added to this bottle. In thisbottle the final active catalyst was form with the ratios ofDTBP/Ti=100, MeOH/Ti=4, MAO/Ti=500. ENB was added as the termonomer forEPDM polymerization.

The 1 L stainless-steel reactor (Fluitron) was baked by flowing nitrogenthrough it for at least one hour and then cooled to 40° C. and thencharged with 500 mL hexane. The mixture made above was transferred bynitrogen overpressure into this reactor. The reactor was sealed and thereactor temperature was brought to 60° C. The reactor was charged withethylene (C₂═) and propylene (C₃═) (C₃═/C₂═ fill ratio of 1:1) until thereactor pressure reached 90 psig (0.62 MPa). The ratio of C₃═ to C₂═ wasthen adjusted to 1:3. The polymerization continued up to 1 h after theintroduction of monomer gases. An aliquot of ENB (0.5 mL) was injectedto the reactor under pressure at polymerization times of 10 min and 30min. Therefore, altogether 3 mL of ENB was charged to thepolymerization.

After the completion of polymerization, 2 mL of ethanol killing solution(0.5 g BHT, 1.0 g Kemamine, 0.5 g Irganox in 125 mL of ethanol) wasinjected to the reactor. The C₂═ and C₃═ flows were shut down and thereactor was vented and cooled to room temperature. The polymer was takenout from the reactor and was blended with methanol and then dried invacuum oven at 40° C. overnight. The recovered polymer weighed 44.8 g,for catalyst activity of 8.96 kg(EPDM)/mmol Ti/h. The polymer has a flowindex (FI) of 0.71.

Comparative Example C5

Similar experiment was carried out as Example 17 except that no methanolsolution was added to (C₅Me₅)TiCl₃. The same amounts of DTBP and MAOwere mixed with (C₅Me₅)TiCl₃. After polymerization, only 0.8 g polymerwas recovered, for catalyst activity of 0.16 kg(EPDM)/mmol Ti/h which is56 times lower than that in Example 17

Example 18

Preparation of Supported Catalyst

In the glovebox under nitrogen, a 200 mL Schlenk® flask was charged withstirbar, 3.01 g porous silica (Davison® 955, previously calcined at 600°C.), and 10 mL MAO in toluene (18 mmol), as well as an additional 5 mLtoluene to aid in agitation. The flask was sealed attached to the vacuumline under nitrogen. In a 100 mL two-necked round-bottom flask wereplaced a stirbar, 4 mL toluene, and 0.619 g 2,6-di-t-butylphenol (DTBP,3.0 mmol). The DTBP solution was transferred into the flask containingthe MAO via cannula and the slurry was stirred for 15 min at roomtemperature. In the glovebox were mixed 0.059 g (C₅Me₅)TiCl₃ (0.2 mmol),10 mL toluene, and 0.032 mL nitrogen-sparged methanol using a stirbar ina third vial. This mixture was transferred into the flask containing theMAO and the resulting red slurry was stirred for an additional 30minutes at room temperature. The toluene was removed in vacuo with mildheat (ca. 40° C.) applied to the flask until a free-flowing powder wasobtained. The solid (4.3 g) was transferred to a glass vial in theglovebox and stored dry. ICP analysis of the catalyst gave titaniumcontent of 0.039 mmol/g, and a molar ratio of Al to Ti of 65.

Polymerization

A 120 mL glass vial was charged with 0.100 g supported catalyst undernitrogen, then additionally charged with 50 mL hexanes (previously driedby 13× molecular sieves and sparged with nitrogen) under nitrogen,followed by 0.25 mL of MAO (1.8 mol/L in toluene). The mixture wastransferred by nitrogen overpressure into the same reactor described inExample 1, which had been dried by flowing nitrogen through it while itwas held at 100° C. for at least 1 h. Following the introduction of thehexane solution of the catalyst mixture, an additional 600 mL driedhexanes were transferred into the reactor. The reactor was sealed andheated to 60° C., where it was held throughout the remainder of the runby a combination of cold water and steam flowed through the reactorjacket. When the reactor had reached approximately 40° C., the reactorwas vented of most of the nitrogen, resealed, and pressurized with 101psig (0.70 MPa) of a mixture of propylene and ethylene, with thepropylene flow made to equal that of ethylene, both measured in L/min.When the reactor had reached within ca. 0.03 MPa of the final pressure,the ratio of propylene to ethylene flows was adjusted to 1:3. Thepolymerization continued until 60 minutes after the introduction ofmonomer gases, at which time 1 mL methanol was injected into the reactorand the reactor was vented and the internal temperature rapidly cooledto room temperature. The polymer was recovered by transfer of thepolymer solution to a large glass beaker, to which were then added ca.500 mL of a 1:1 mixture by volume of methanol and 2-propanol. Therecovered polymer weighed 18.4 g, for a catalyst activity of 4.7kg(EPR)/(mmol(Ti).h). The polymer contained 49.1 weight % propylene byIR spectroscopy and had FI=5.9. SEC found the M_(w) =267,400, withPDI=3.6. DSC on the polymer revealed a crystallinity of 0.33% on firstheat and a PRT of −30.0° C.

Example 19

The procedures and conditions used in Example 18 were repeated using thesame catalyst, with the exception that 3 mL ENB were added to the 120 mLflask prior to transfer into the reactor. The recovered polymer weighed7.8 g, for a catalyst activity of 2.0 kg(EPR)/(mmol(Ti).h). The polymercontained 45.1 weight % propylene and 1.8 weight % ENB by IRspectroscopy and had FI=1.8. SEC found the M_(w)=244,800, with PDI=2.7.DSC on the polymer revealed a crystallinity of 0.36% on first heat and aPRT of −29.4° C.

Example 20

Preparation of Supported Catalyst

In the glovebox under nitrogen, a 200 mL Schlenk® flask was charged withstirbar, 3.02 g porous silica (Davison® 955, previously calcined at 600°C.), and 10 mL MAO in toluene (18 mmol), as well as an additional 5 mLtoluene to aid in agitation. The flask was sealed attached to the vacuumline under nitrogen. In a 100 mL two-necked round-bottom flask wereplaced a stirbar, 4 mL toluene, and 0.787 g 2,4,6-tri-t-butylphenol(TTBP, 3.0 mmol). The TTBP solution was transferred into the flaskcontaining the MAO via cannula, along with an additional 5 mL toluenerequired to complete the transfer, and the slurry was stirred for 15 minat room temperature. In the glovebox were mixed 0.058 g (C₅Me₅)TiCl₃(0.2 mmol), 5 mL toluene, and 0.032 mL nitrogen-sparged methanol using astirbar in a third vial. This mixture was transferred into the flaskcontaining the MAO, along with an additional 5 mL toluene required tocomplete the transfer, and the resulting red slurry was stirred for anadditional 30 minutes at room temperature. The toluene was removed invacuo with mild heat (ca. 40° C.) applied to the flask until afree-flowing powder was obtained. The solid (4.39 g) was transferred toa glass vial in the glovebox and stored dry. ICP analysis of thecatalyst gave titanium content of 0.032 mmol/g, and a molar ratio of Alto Ti of 81.

Polymerization

The same procedures and conditions described in the polymerizationsection of Example 18 were followed, except that 0.100 g of the catalystdescribed in Example 20 was used in place of that of Example 18. Therecovered polymer weighed 13.6 g, for a catalyst activity of 4.3kg(EPR)/(mmol(Ti).h). The polymer contained 47.0 weight % propylene byIR spectroscopy and had FI=2.6. SEC found the M_(w)=254,800, withPDI=3.4. DSC on the polymer revealed a crystallinity of 0.60% on firstheat and a PRT of −28.9° C.

Example 21

The procedures and conditions used in Example 20 were repeated using thesame catalyst, with the exception that 3 mL ENB were added to the 120 mLflask prior to transfer into the reactor. The recovered polymer weighed3.5 g, for a catalyst activity of 1.1 kg(EPR)/(mmol(Ti).h). The polymercontained 44.2 weight % propylene and 1.5 weight % ENB by IRspectroscopy. SEC found the M_(w)=251,400, with PDI=3.0. DSC on thepolymer revealed a crystallinity of 0.87% on first heat and a PRT of−16° C.

Example 22

Polymerization in the Fluidized Gas-Phase Reactor

A fluidized-bed gas-phase polymerization reactor, as described in U.S.Pat. No. 4,588,790, of 14″ (35.6 cm) diameter is charged with 100 lb(45.4 kg) polyethylene (0.918 g/cm³) and 10 lb (4.5 kg) carbon black anddried under flowing nitrogen while held at at least 80° C. for at least8 hours. The temperature of the reactor is dropped to 60° C. The reactoris pressurized to 300 psig (2.11 MPa) with a mixture of gases such thatthe partial pressures of the gases are in the following ratios:ethylene:propylene:nitrogen=1:0.7:1. ENB (50 mL) is charged into thereactor. The reactor gases are continuously cycled through the reactorat a linear velocity in the reaction zone of 53 cm/sec. A solution ofmethylalumoxane (100 mL of a 1.8 moles(Al)/L in toluene) is injectedinto the bed. One half-hour later, a solution of (C₅Me₅)TiCl₃ andmethanol in toluene (0.007 moles(Ti)/L, molar ratio of methanol:Ti=4:1),which has been stirred for at least 15 minutes, is contacted with astream of a mixture of methylalumoxane and DTBP in toluene (such thatthe final concentration is 1.2 moles(Al)/L and the DTBP:Al molar ratiois 1:5) in a volumetric ratio of titanium solution to alumoxane/tritox-Hsolution of 1:3. The mixture of (C₅Me₅)TiCl₃, methanol, alumoxane, DTBPand toluene is pumped through a coil of sufficient length to provide atleast 10 minutes of residence time before the activated catalystsolution is then taken up by a nitrogen stream and passed into thereactor through a metal tube (3.2 mm outer diameter) which penetratesthe reactor wall at a point 1 ft (30.5 cm) above the distributor plate.Catalyst is injected into the reactor at the rate of 1.0 mmol titaniumper hour. At the first sign of reaction, a flow of ENB is establishedsuch that the weight of ENB introduced per unit time is 7% of the sum ofthe weights of ethylene and propylene consumed per unit time. At thefirst sign of reaction, carbon black is fed to the reactor such that theweight of carbon introduced per unit time is 30% of the sum of theweights of ethylene and propylene consumed per unit time. The amount ofpolymer and carbon black in the reactor is maintained at a total ofapproximately 50 kg. Unagglomerated product is dischargedsemi-continuously from the reactor at a rate equal to the sum of therate of polymer production and the rate of carbon black addition (inweight units) into a chamber normally isolated on both ends by valves,where the product is vented of excess monomers and nitrogen, and is thenpurged with nitrogen and discharged to an accumulation drum, where it ispurged with nitrogen saturated with moisture. The reactor is then run inthis manner for 24 hours with an average EPDM polymer production rate of20 lb/hour (9.1 kg/hour) with no significant fouling, as evidenced byreactor inspection during cleaning.

Example 23

Ethylene-1-hexene Copolymerization

A small glass vial was charged with magnetic stirbar and a toluenesolution of (C₅Me₅)TiCl₃ (0.0031 mmol/L) and methanol (0.0125 mmol/L),which was stirred at room temperature for ca. 4 hours. A glass bottleequipped with stirbar was then charged with 50 mL hexanes undernitrogen, followed by 1.25 mmol of MAO as toluene solution, followed by1.6 mL of a solution of 0.626 g DTBP dissolved in 20 mL toluene (0.25mmol tritox-H). The mixture then was transferred by nitrogenoverpressure into the 1.3 L reactor which had been dried by flowingnitrogen through it while it was held at 100° C. for at least 1 hour(h). Following the introduction of the hexane solution of the MAO/DTBPmixture, a mixture of 50 mL 1-hexene and 600 mL hexanes were transferredinto the reactor. The reactor was then sealed and heated to 75° C. andpressurized with 153 psig (1.06 MPa) of ethylene. Following this, .08 mL(C₅Me₅)TiCl₃/methanol solution (0.0025 mmol Ti) were injected directlyinto the reactor via syringe. The temperature then proceeded to reach111° C. and stayed above 100° C. for the remainder of the run, at whichpoint (5 min total polymerization time) reaction was terminated byinjection of 1 mL methanol and venting of the gases. The reactortemperature was rapidly cooled to room temperature. The polymer wasrecovered by transfer of the polymer solution to a large glasscrystallization dish, where it was air-dried overnight followed bydrying in a vacuum oven for at least 16 h. The recovered polymer weighed41.6 g, for a catalyst activity of 200 kg(PE)/(mmol(Ti).h). The polymerdensity was 0.8752 g/cm³, while the FI=9.1.

TABLE I Additive 1 Additive 2 Cocatalyst Run Example* Catalyst (mmol)(eq.) (eq.) (eq.) time, h 1 (C₅Me₅)TiCl₃ (1) MeOH (4) DTBP (100) MAO(1000) 0.5 2 (C₅Me₅)TiCl₃ (1) MeOH (4) DTBP (100) MAO (1000) 0.5 3(C₅Me₅)TiCl₃ (1) MeOH (4) DTBP (100) MAO (1000) 0.5 4 (C₅Me₅)TiCl₃ (1)MeOH (4) DTBP (100) MAO (1000) 0.5 5 (C₅Me₅)TiCl₃ (1) MeOH (4) DTBP(200) MAO (1000) 0.5 C1 (C₅Me₅)TiCl₃ (1) none DTBP (200) MAO (1000) 0.56 (C₅Me₅)TiCl₃ (5) MeOH (4) DTBP (100) MAO (500) 0.67 C2 (C₅Me₅)TiCl₃(5) none DTBP (100) MAO (500) 0.67 7 (C₅Me₅)TiCl₃ (5) MeOH (4) DTBP(100) MAO (500) 0.67 C3 (C₅Me₅)TiCl₃ (5) none DTBP (100) MAO (500) 0.678 (1,3-TMS₂Cp)TiCl₃ (5) MeOH (4) DTBP (100) MAO (500) 1 9 (C₅Me₅)TiCl₃(5) MeOH (4) DTBP (100) MAO (500) 0.25 10 (C₅Me₅)TiCl₃ (1) MeOH (4) BHA(100) MAO (1000) 0.5 11 (C₅Me₅)TiCl₃ (1) MeOH (4) BHT (100) MAO (1000)0.5 C4 (C₅Me₅)TiCl₃ (1) none BHT (100) MAO (1000) 0.5 12 (C₅Me₅)TiCl₃(2) MeOH (4) BHT (100) MAO (1000) 0.5 13 (C₅Me₅)TiCl₃ (1) MeOH (4) TBC(100) MAO (1000) 0.5 14 (C₅Me₅)TiCl₃ (1) MeOH (4) TTBP (100) MAO (1000)0.5 15 (C₅Me₅)TiCl₃ (1) MeOH (4) TTBP (100) MAO (1000) 0.5 16(C₅Me₅)TiCl₃ (1) MeOH (4) TTBP (100) MAO (1000) 0.5 17 (C₅Me₅)TiCl₃ (5)MeOH (4) DTBP (100) MAO (500) 1 C5 (C₅Me₅)TiCl₃ (5) none DTBP (100) MAO(500) 1 Pressure Pressure scav. ENB, C₃= :C₂= , C₃= :C₂= , Example*(psi) (MPa) (mL) mL fill feed Yield, g 1 101 0.70 none 0 1:1 1:3 11.6 2125 0.86 none 0 1:1 1:3 13.1 3 102 0.70 none 3 1:1 1:3 9.4 4 104 0.72none 0 8:1 1:1 18.6 5 102 0.70 none 0 1:1 1:3 30.0 C1 103 0.71 none 01:1 1:3 27.7 6 102 0.70 none 0 1:1 1:3 59.6 C2 102 0.70 none 0 1:1 1:330.0 7 102 0.70 none 5 1:1 1:3 61.6 C3 102 0.70 none 5 1:1 1:3 55.3 8101 0.70 none 0 1:1 1:3 41.5 9 ca. 45 ca. 0.31 none 0 1:0 1:0 33.4 10104 0.72 none 0 1:1 1:3 0.5 11 113 0.78 none 0 8:1 1:3 2.7 C4 111 0.77none 0 8:1 1:3 1.1 12 125 0.86 TiBA 0 8:1 1:3 <0.1 (0.5) 13 110 0.76none 0 8:1 1:3 1.2 14 105 0.72 none 0 8:1 1:3 12.2 15 103 0.71 none 01:1 1:3 4.7 16 104 0.72 none 3 8:1 1:3 2.7 17  90 0.62 none 3 1:1 1:344.8 C5  90 0.62 none 3 1:1 1:3 0.8 13 1_(H) activity, IR data IR data Cnmr nmr tot xtal kg(polymer)/ C3=, ENB, C3= , ENB, Mw/1000 (1st Example(mmol(Ti) · h) wt % wt % wt % wt % FI (PDI) heat) PRT 1 23.2 43 38.90.36 420.1 (2.80) 0.83 −21.3 2 26.2 43 0.41 1.02 −24.7 3 18.8 39 2.336.7 0.22 0.11 −21.3 4 37.2 78 83.2 5.7 239.3 (2.32) 0 n/a 5 60.0 440.43 0.14 −12.9 C1 55.4 45 0.58 0.16 −30.2 6 17.8 65 1.0 0 none C2 9.044 1.0 0.48 −13.1 7 18.4 62 5.9 1.6 0 none C3 16.5 0.7 0 −35.3 8 8.3 4222.8 0 −48.5 9 26.7 0.43** 10 1.0 47 11 5.4 79.6 274 (4.2) C4 2.2 223(2.74) 12 <0.1 13 2.4 66 193 (2.73) 14 24.4 62 67.4 9.3 225.3 (2.31) 0−23.1 15 9.4 37 41.9 0.74 345.6 (2.66) 0.39 −15.6 16 5.4 70 12.6 73.92.1 0.47 −21.7 17 9.0 0.71 C5 0.2 *All runs conducted in 650 mL hexanesat 60° C., except for Example 17 and Comparative example C5, which wererun in 500 mL hexanes. **melt flow measured at 230° C. under 2.1 kgload; all other flow indices measured at 190° C. under 21 kg load.

What is claimed is:
 1. A process for the polymerization of at least oneolefin which comprises contacting said olefin under polymerizationconditions with a catalyst comprising: (A) a transition metal compoundhaving the formula: (C₅R¹ ₅)MX₃, wherein each R¹ substituent isindependently selected from the group consisting of hydrogen, a C₁-C₈alkyl, an aryl, and an aryl heteroatom moiety or alkyl heteroatom moietywith the proviso that no more than three R¹ substituents are hydrogen;and wherein two or more R¹ substituents may be linked together forming aring; M is a transition metal of Group IVB of the Periodic Table of theElements; and X is a halide atom; (B) a compound having the formula:R²OH, wherein R² is a C₁-C₈ alkyl; (C) a bulky phenol compound havingthe formula: (C₆R³ ₅)OH, wherein each R³ group is independently selectedfrom the group consisting of hydrogen, halide, a C₁-C₈ alkyl, an aryl, aheteroatom substituted alkyl or aryl, wherein two or more R³ groups maybe linked together forming a ring, and in which at least one R³ isrepresented by a C₃-C₁₂ linear or branched alkyl located at either orboth the 2 and 6 position of the bulky phenol compound; and (D) analuminoxane.
 2. The process of claim 1 wherein the catalyst additionallyemploys a support or spray drying material.
 3. The process of claim 1wherein an inert particulate material is employed as fluidization aid.4. The process of claim, 1 wherein the polymer produced is selected fromthe group consisting of polyethylene, polypropylene, an ethylene-alphaolefin copolymer, and an ethylene-alpha olefin-diene terpolymer, apropylene copolymer.
 5. A polymer produced by the process of claim 1.